Halo triazines



United States Patent HALO TRIAZINES Hansiuergen Schroeder and Christoph J. Grundmann, Columbus, Ohio, assiguors to Olin Mathieson Chemical Corporation, a corporation of Virginia No Drawing. Application August 22, 1955 Serial N0. 529,928

15 Claims. (Cl. 260-248) Our invention relates to novel 2,4-bis(alkyl and haloalkyl substituted)-6-halo-1,3,5-triazines of the general formula:

wherein R is an alkyl or haloalkyl radical and X is a halogen. Preferred alkyl radicals are the lower alkyl radicals having from 1 to 4 carbon atoms, i.e., methyl, ethyl, propyl and butyl, although alkyl radicals containing up to 12 carbon atoms are included in the scope of this invention. X and the halogen derivatives of the alkyl radicals include fluorine, bromine, chlorine and iodine. The haloalkyl radicals include, for example, monochloromethyl, dichloromethyl, trichloromethyl and (where 11:0 to 12) and the corresponding fluorine, bromine and iodine derivatives. Our novel compounds are useful as fungicides and intermediates.

We have found that 2,4-bis(alkyl or haloalkyl)-6-halo- 1,3,5-triazines can be efi'iciently prepared by reacting phosphorus oxyhalides, preferably phosphorus oxychloride or phosphorus oxybromide, with 2,4-bis(alkyl)-6-hydroxy- 1,3,5-triazines or the double salts of 2,4-bis(alkyl or haloalkyl)-6-hydroxy-1,3,5-triazine with amidines. The 2,4- bis(alkyl)-6-hydroxy-1,3,5-triazines are described and claimed in our co-pending application Serial No. 532,120, filed September 1, 1955. The amidine salts are described and claimed in our co-pending application, Serial No. 529,927, filed August 22, 1955. The amidine salts have the formula:

wherein R is an alkyl or haloalkyl radical. The saltsin which R is haloalkyl are prepared by the reaction of phosge'ne with haloalkyl amidines. The salts in which R is alkyl are formed from the haloalkyl compounds by catalytic hydrogenolysis of the haloalkyl groups to alkyl groups. In preparing the compounds of our invention the HCl formed. After a few hours refluxing, much of the excess phosphorus. oxyhalide is suitably removed by distillation and the halotriazine is recovered by crystallization. It is suitably purified by recrystallization.

In use as fungicides, the novel compounds of our invention are suitably formulated as dusts, wettable powders, emulsifiable concentrates or solutions. Siliceous clays in finely divided form are suitable diluents for dusts. An example of such a fungicidal dust is an intimate mixture of about 5 percent of one of our compounds uniformly dispersed on percent of attapulgite. A 50 percent wettable powder can be prepared containing 50 perwherein R is an alkyl or haloalkyl radical and R and R, are hydro-gen, aryl or alkyl groups or alkylene groups linked together, by reaction with ammonia, primary or secondary amines of the formula:

wherein R and R are hydrogen, aryl or alkyl groups or alkylene groups linked together, e.g., ethylenimine, as described and claimed in our pending application Serial No. 529,929, filed August 22, 1955.

The compounds of our invention, their preparation and usefulness will be illustrated by the following examples:

Example I (A) The crude 2,4-bis(trichloromethyl)-6-hydroxy-l, 3,S-triazine-trichloroacetamidine salt (30 grams) and POCl (75 grams) were refluxed at a bath temperature of C. for three hours, after which excess POCI was removed by distillation in vacuum and the remaining viscous residue was triturated with a mixture of ice and water whereupon it formed a solid. The product was dried over P 0 in vacuo and then extracted with Skellysolve. The solution was filtered and evaporated to recrystallize 2,4-bis(trichloromethyl)-6-chloro 1,3,5 triazine. The yield was 21 grams or 98 percent of the theory of the product which melted at 56 C.

(B) The fungicidal properties of 2,4-bis(trichloromethyl)-6-chloro-1,3,5-triazine were determined on four different fungi according to the following procedure:

Threads were infested with a 10 day old culture of a particular fungus. These threads were then treated with (undiluted) 2,4-bis(trichloromethyl)-6-chloro,1,3,5 triazine and transferred to potato dextrose agar plates. Af-

Pate'nted Mar. 31, 1950 solved-in 25 milliliters of ether.

ter 7 days, the number of new colonies was observed. The results are tabulated below:

' New Fungus Colonies After 7 days Bohr ii cinema. Colletqtrichum 0 Fusanum ozysporum lucopersici 0 Rhizoc lontn solzmi 0 The appearance of no new colonies indicates complete control over these fungi.

(C) A solution of 2 grams of the 2.4-bis(trichloromethyl)-6-chloro-1,3,5-triazine in 20 milliliters of ether was added at 0 C., to lgram of dimethylamine dis- Dimethylamine hydrochloride separated and was filtered off. The filtrate was evaporated in vacuum and the 2,4-bis-(trichloromethyl)- 6-dimethylamino-1,3,5-triazine was recrystallized from Skellysolve. The yield was 1.8 grams or 89 percent of the theory of product which melted at 120 C.

C H N Cl Calculated [or enamel, Found Example II (A) According to the procedure of Example I(A),

10 grams of '2,4-bis(dichloromethyl)-6-hydroxy-l-,3, 5-triazine-dichloroacetamidine salt were chlorinated with 30. grams of POCl to produce 2,4-bis-(dichloromethyl)- 6-chloro-l,3.5-triazine. The yield was 5.5 grams, or 72 percent of the theory, of product which melted at 114 C.

c H N or Calculated for CH2N3C15 Z2 14. 631712 8 15. 62. 5 Fmmd 21.41 0.77 14.99 62. 14

(B) According to the procedure of Example [(8), 1 gram of 2,4-bis(dichlormethyl)-6-chloro-1,3,5-triazine was aminated to form 2,4-bis-(dichloromethyl)-6-dimethylamino-l,3,5-triazine. The yield was 850 milligrams, or 82 percent of the theory, of product which melted at 78 C.

C H N C1 Calculated for C1HsN4Cl 29.00 2 78 19. 32 48. 91 Found 29.36 2 82 19.18 48.87

Example III Calculated for osHtNsoh 2s. 2s 1. s9 19. 71 50.06 Found 2s. 35 2. 23 19. 74 49. e3 28. 16 2. 42 19.81 49. 75

Example IV (A) A mixture of 1 gram of 2,4-dimethyl 6-hydroxy- 1,3,5-triazine-acetamidine salt, 1 gram of triethylamine, and 8 grams of POCl were refluxed for one-half hour.

The excess of POCl and the dimethylchloro-triazine were then removed by distillation. The 2,4-dimethyl-6-chlora 1,3,5-triazine crystallized in the condenser and, after cooling, in the distilled P0Cl After filtering off from the POCl it was dissolved in ether, filtered, and the ethereal solution evaporated. The residue was recrystallized from Skellysolve, and the yield was 270 milligrams or 35 percent of the theory of 2,4-dimethyl-6-chloro-l,3,5-triazine which melted at 64 C.

O H N C1 Calculated for csflaNlCi a 2a a a .7 Fmmd i 41. 59 4.35 29.30 24. 65

halo-1,3,5-triazine of the formula.

in which R is selected from the group consisting of, alkyl and haloalkyl radicals and X is a halogen, which comprises reacting 2,4-bis(substituted)-6-hydroxy-l,3,S-triazine amidine salts of the formula in which R is selected from the group consisting of alkyl and haloalkyl radicals containing not more than 12 carbon atoms, with a phosphorus oxyhalide at a temperature of about to 200 C. and in proportions and for a time effective to produce the 6-halo-triazines.

6. The process of claim 5 in which R is chloroalkyl and the oxyhalide is an oxychloride.

7. The process of preparing 2,4-bis(trichloromethyl)- 6-chloro-l,3,5-triazine which comprises reacting 2,4-bis (trichloromethyl) 6 hydroxy 1,3,5 triazine trichloroacetamidine salt with phosphorus oxychloride at a temperature of about 100 to 200 C. and in proportions and for a time efiiective to produce the 6-chlorotriazine.

8. The process of preparing 2,4-bis(dichloromethyl)- 6-chloro-1,3,5-triazine which comprises reacting 2,4-bis (dichloromethyl) 6 hydroxy 1,3,5 triazine dichloroacetamidine salt with phosphorus oxychloride at a temperature of about 100 to 200 C, and in proportions and for a time effective to produce the 6-chloro-triazine.

9. The process of preparing 2,4-bis(monochloromethyl)-6-chloro-1,3,5-triazine which comprises reacting 2,4 bis(monochloromethyl) 6 hydroxy-l,3,5-triazinemonochloroacetamidine salt with phosphorus oxychloride at a temperature of about 100 to 200 C. and in proportions and for a time effective to produce the 6-chlorotriazine.

10. The process of claim in which R is an alkyl radical and the oxyhalide is an oxychloride.

11. The process of preparing 2,4-dimethyl-6-chloro- 1,3,5-triazine which comprises reacting 2,4-dimethyl-6- hydroxy-1,3,5-triazine-acetamidine salt with phosphorus oxychloride at a temperature of about -100 to 200 C. and in proportions and for a time efiective to produce the 6-chloro-triazine.

12. The process of preparing 2,4-bis(substituted)-6- halo-1,3,5-triazine of the formula in which R is an alkyl radical and X is a halogen, which comprises reacting 2,4-bis(alkyl)-6-hydroxy-1,3,5-triazine in which the alkyl group contains not more than 12 carbon atoms with a phosphorus oxyhalide at a temperature of about 100 to 200 C. and in proportions and for a time efiective to produce the 6-ha1o-triazines.

13. The process of preparing 2,4-dimethy1-6-chloro- 1,3,5-triazine which comprises reacting 2,4-dimethyl-6- hydroxy-1,3,5-triazine with phosphorus oxychloride at a temperature of about 100 to 200 C. and in proportions and for a time effective to produce the 6-chloro-triazine.

14. 2,4-bis(haloalky1)-6-halo-1,3,5-triazine in which the alkyl group contains not more than 12 carbon atoms,

'15. The process of preparing 2,4-bis(substituted)-6- halo-1,3,5-triazine of the formula in which R is selected from the group consisting of alkyl and haloalkyl radicals and X is a halogen, which comprises reacting a hydroxy-triazine selected from the group consisting of (1) 2,4-bis(substituted)-6-hydroxy-1,3,5- triazine amidine salts of the formula References Cited in the file of this patent UNITED STATES PATENTS 2,537,816 Dudley Jan. 9, 1951 2,653,934 Kaiser Sept. 29, 1953 2,691,018 Joyce Oct. 5, 1954 2,810,706 Frazier Oct. 22, 1957 

1. 2,4-BIS(CHLOROALKYL)-6-CHLORO-1,3,5-TRIAZINE IN WHICH THE ALKYAL GROUP CONTAINS NOT MORE THAN 12 CARBON ATOMS,
 5. THE PROCESS OF PREPARING 2,4-BIS(SUBSTITUTED)-6HALO-1,3,5-TRIAZINE OF THE FORMULA 